Water dispersible methylolamide products



Lester P. Hayes, 1833 W. Sunset, Decatur, Ill. 62522 No Drawing.Continuation of application Ser. No.

264,069, Mai. 11, 1963, which is a continuationin-part of applicationSer. No. 245,973, Dec. 20, 1962. This application June 5, 1967, Ser. No.643,367

Int. Cl. C0815 11/00; C08g 9/20; 'C09j 3/16 U.S. Cl. 260-21 38 ClaimsABSTRACT OF THE DISCLOSURE I Methylol amides of an adduct of a maleylcompound and an aliphatic compound containing an ethylenicallyunsaturated fatty chain of from '0 to 24 carbon atoms, their preparationand use in pai ts, warp-sizing compositions, non-woven binders,adhesives, lubricants, etc.

This invention relates to a new class of compounds which are methylolamides of adducts formed from alpha, beta-ethylenically unsaturateddicarboxy compounds and ethylenically unsaturated fatty compounds havinga chain of at least 10 carbon atoms. More specifically; this inventionrelates to water-soluble methylol amides of maleated oils, which can becured by heat to form water-resistant layers.

Various adducts of long chain ethylenically unsaturated fatty materialsand alpha, beta-ethylenically unsaturated dicarboxy compounds (thealpha, beta-ethylenically unsaturated dicarboxy compounds are alsoreferred to as maleyl compounds) have been describe-d. See, for example,U.S. Patents 2,033,131; 2,033,132 and 2,063,540 to Ellis; US. Patents2,188,882-90 and 2,285,646 to Clocker; 2,342,113 to Blair et al.;2,423,230; 2,455,743 and 2,462,618 to Eilerman; 2,640,814 to Schmutzler;2,678,934 to Grummit; 2,491,968 to McKenna; 2,967,837 to Greenfield;3,015,566 to Becker et al.; 3,030,321 to Lombardi; etc. For the mostpart, these references have been directed principally to the so-calledmaleated or maleinized oils.

This application is a continuation of forfeited applica- .tion Ser. No.264,069, filed Mar. 11, 1963, which is a continuation-in-part offorfeited application Ser. No. 245,973, filed Dec. 20, 1962.

These products have engendered considerable interest because of the casewith which the adducts form, the almost quantitative yields, theavailability and low cost of the oils and maleic anhydride, etc.

However, US. Patents 2,941,968 and 3,030,321 point out that the priorart products, when dispersed in water with or without other ingredients,were unsatisfactory since the products were unstable in aqueous medium.The unstable materials could not be stored for any great length of timebecause the dispersed resin component or other vehicle components, suchas drying oils, settled-out or de-emulsified. Further, films formed fromthe conventional dispersions were also characterized by a lack ofhardness and toughness. Likewise, their resistance to washing and to theaction of solvents was unduly low. US. Patents 2,941,968 and 3,030,321considered that these problems could be solved by the free radicaladdition polymerization of one or more vinylidene monomers with themaleated oils or modified maleated oils.

The general object of this invention is to provide a new class ofcompounds which are methylol amides of adthe -15 C RUSI'SR'EFEBEENCESEARC 3947194655 v 7,, 5' 7 seats United Patented Oct. 7, 1969 ductsformed from alpha, beta-ethylenically unsaturated 3,471,466 dicarboxycompounds and ethylenically unsaiuriated com- WATER SE g E pounds havinga chain. of at least 10 carbon atoms. A

somewhat more specific object of this inventionis to pro vide stablewater-dispersible methylol amides of adducts resulting from the reactingof ethylenically unsaturated long chain fatty esters, amides, acids orsalts and alpha, beta-ethylenically unsaturated dicarboxy compounds,which can be cured to a water-resistant material by heating, A stillmore specific object of this invention is to provide water-solublemethylol amides of maleated oils which can be cured to awater-resistant, detergent-resistant material by heating.

In one aspect, this invention is a class of fatty compounds, which canbe represented by the structure:

wherein CHZOR;

wherein the various symbols are as defined above.

In a second aspect, this invention is a process of making methylolamides which comprises reacting formaldehyde with an amide adduct of analpha, beta-ethylenically unsaturated dicarboxy compound and anethylenically unsaturated compound having a chain ofat least 10 carbonatoms.

In a third aspect, this invention is a process of providing methylolamides, which comprises the steps of (1) forming an adduct of an alpha,beta-ethylenically unsaturated dicarboxy compound and an ethylenicallyunsaturated compound having a chain of at least 10 carbon atoms, (2)reacting said adduct with a nitrogen containing basic materialnamhthen(3) reacting the reaction product of step (2) with formaldehyde to forma methylol amide.

In a fourth aspect, this invention is an aqueous dispersion of amethylol amide adduct of an alpha, beta-ethylenically unsaturateddicarboxy compound and an ethylenically unsaturated long chain fattycompound having a chain of at least carbon atoms.

In another aspect, this invention is a process of formingwater-resistant coatings which comprises applying an aqueous solution ofa methylol amide described in the preceding paragraphs to a substrateand heating the applied coating to cure it.

In the description that follows, a variety of methylol amide adducts aredescribed. All of these products can be used interchangeably with moreor less success when the utility of the compound is based principallyupon the physical properties of the methylol amide and not upon how themethylol amide adduct cures or the actual properties of the curedmethylol amide adduct. For example, the adducts of this invention areuseful in warp sizing compositions because of their lubricating actionand in varous emulsions because of their dispersing properties. On theother hand, the versatile and useful methylol amides of this inventionare dependent upon the final properties of the cured methylol amides,such as Waterresistance, detergent resistance, organic solventresistance, tensile strength, freedom from tack, etc. Inasmuch as one ofthe principal objects of this invention is to provide water-solublemethylol amide adducts whose cured products form water-resistant,detergent resistant materials, the description that follows emphasizesthe method for providing methylol amides of this type.

In the description that follows the words dispersing and dispersion areused in a generic sense to be inclusive of the words suspending,dissolving, suspension and solution. The words ammonia and ammoniumhydroxide are useful interchangeably. The term formalde=- hyde is usedin a generic sense to be inclusive of monomeric formaldehyde andformaldehyde-generating materials.

REACTION MECHANISM AND PRODUCTS Inasmuch as the various reactions takingplace in the processes of this invention are relatively complex andsince the reaction products themselves are dependent upon the choice ofreactants, it is advisable to consider first the stepwise reaction ofthe ethylenically unsaturated fatty material with the preferred alpha,beta-ethylenically unsaturated dicarboxy compound (maleic anhydride),the preferred source of basic nitrogen (ammonia or ammonium hydroxide)and the preferred source of formaldehyde (monomeric formaldehyde). Thereasons why these materials are preferred will become apparent later inthe specification.

In accordance with the invention, heating of a long chain fattyethylenically unsaturated compound, such as soybean oil or linseed oil,with a maleyl compound, e.g., maleic anhydride, results in an additionreaction between the ethylenic group of the dicarboxy compound and thehydrogen atom alpha to an ethylenic group in the long chain fattycompound. In this reaction, the ethylenic group of unsaturated dicarboxycompound becomes saturated while the double bonds of the long chainfatty compound remain unsaturated. For example.

BOHQOH=OHOHA In the event that conjugated unsaturated long chain fattycompounds such as tung oil or compounds capable of isomerizing underreaction conditions to give conjugation (such as soybean oil or linseedoil), are present, a Diels-Alder type of reaction also occurs. Forexample,

Both types of reaction are herein termed addition reactions or adductreactions since neither involves removal of water. This step is alsoreferred to herein as the maleation step. Other reactions may occur to alimited extent and are not precluded.

The adducts are then converted to the amide form by reaction with abasic nitrogen compound, e.g., ammonia. For example,

BCH2CH=CH H-A When an anhydride is employed as the ethylenicallyunsaturated dicarboxy compound or an anhydride is formed during themaleation reaction, the anhydride ring of the adduct may be opened byboiling the addition products with water. Subsequently, the freecarboxylic acid groups can be neutralized with certain compoundscontaining a basic nitrogen atom sometimes referred to hereafter asbasic nitrogen compounds. The resultant products are water-dispersible.If the starting long-chain fatty compound contains free carboxylic acidgroups, these groups will also be converted to amide and ammonium saltgroups. This step is referred to as the amide-forming step. The amideadducts are then reacted with formaldehyde, preferably in aqueoussolution, to form methylol amide groups. At the same time the ammoniumions in the aqueous solution are converted to various amide-aldehydeproducts, such as hexamethylene tetramine. This side reaction causes thereaction product to become acidic. If sufficient formaldehyde is addedto the reaction product, the methylol amide adduct precipitates from theaqueous medium.

BCHzCH2-CH=CH( JH-A C5H12N5 The methylol amide adduct, if precipitated,is then redispersed by the addition of additional ammonia. The freecarboxyl groups of the methylol amide are thereby converted again to theammonium salt form.

THE LONG CHAIN ETHYLENICALLY UNSATURATED COMPOUND In somewhat greaterdetail, the divalent aliphatic group B( 3H-CH=CH-( lHA can obtainvarious other groups such as carboxyl groups, halo groups, acyloxygroups, alkoxy groups, aryloxy groups, tertiary amino or quaternaryammonium groups, etc. The preferred long-chain ethylenically unsaturatedcompounds of this invention are the readily available naturallyoccurring polyunsaturated glyceride oils (which are considered as havingcarboxylate groups) having from to 24 carbon atoms in the unsaturatedlong chain, such as soybean oil, corn oil, cottonseed oil, hempseed oil,tung oil, oiticica oil, safiiower oil, peanut oil, linseed oil, tobaccoseed oil, cod oil, herring (or menhaden) oil, dehydrated castor oil,etc. The glyceride oils and the esters of other unsaturated long chainacids, such as the linoleic acid esters of trimethylol propane and talloil fatty acid esters of pentaerythritol, are preferred since theycontain a relatively large number of ethylenic double bonds available assites for adduct formation. In general, those compounds having on anaverage at least two and preferably three to nine ethylenicallyunsaturated groups per molecule are preferred. As may be apparent fromthe aforementioned discussion, two conjugated ethylenic double bonds(see Equation II) are equivalent to only a single unconjugated ethylenicdouble bond (see Equations I and II) since two conjugated double bondsand the single unconjugated double bond each serve as a single site foradduct formation.

Instead of the glycerides, various tertiary amines, quaternary aminesand amides having a plurality of longchain unsaturated radicals alsooffer the advantage of plural unsaturation, but at a relatively highcost. As explained below, the various properties of the methylol amideadducts of this invention are dependent upon the average number ofmethylol amide groups and carboxylate salt groups formed in the fattymolecule amide groups the higher the concentration of methylol amidegroups and carboxylate salt groups in the fatty molecule, the better thefilm properties (tensile strength and solvent resistance) of appliedcoatings based on the compounds of this invention. These methylol amidegroups and carboxylate salt groups are sometimes referred to below aspotentially reactive carboxy groups. This term also includes the freecarboxylic acid group, the anhydride group and the amide group, but doesnot include esterified car= boxy groups. The number of potentiallyreactive carboxy groups also controls the dispersibility of the methylolamide adducts in aqueous ammonium hydroxide. Generally, the methylolamides based on fatty compounds having a plurality of long-chainunsaturated fatty radicals are soluble in ammoniacal solutions if themethylol amide adduct contains on an average at least about 1potentially reactive carboxy group per each long chain fatty radical offrom 10 to 24-carb0n atoms.

Fatty acids, such as oleic acid, linoleic acid and linolenic acid, andsalts thereof are only somewhat less preferred than the above esters.While these fatty compounds do not contain as many sites for adductformation as the above esters, the presence of the free acid group orsalt group compensates to some extent for the smaller number ofpotential adduct sites. The methylol amide adducts formed from thesecompounds have excellent properties as additives to yarn sizingcompositions. In some cases, it is desirable to employ mixtures ofmethylol amide adducts derived from both fatty acids and the aboveesters, particularly the glyceride esters, in order to give the curedmethylol amides additional desirable properties, such as increasedflexibility and better elongation.

The N-unsubstituted amides of acids, such as linoleic acid, linolenicacid and oleic acid, are quite similar to the acids of the precedingparagraph except that they are somewhat more expensive. However, this iscompensated for by the fact that a substantial number of the carboxygroups of the starting fatty amide are converted to meth ylol amidegroups in the process of this invention while only a relatively smallproportion of the carboxy groups of the fatty acids and salts thereofare converted to the methylol amide form.

The following are representative of other ethylenically unsaturatedcompounds, which can be used in this invention: 1-chlorodecene-4;l-bromooctadecene-9; l-chlorotetracosene-9; l-nitrilooctadecene;N,N-dimethyl-linole= amide; N,N-linoleimide; N,N-linolenimide;N,N-dimethyl N,Ndilinoleylamine; N-methyl-N,N-dilinoleylamine;10-carboxyldecene-2; l-acetoxyoctadecene-4j l-phenoxy octadecene-9;1-propoxyoctadecene-9; etc.

When the divalent group B(IIH-CH1=OH-(JJH-A of the methylol amide adductis substituted by a carboxylate group, the substituent can berepresented by the formula: Y

O O )0'Z(O( )RB)n wherein Z is the residue of a hydroxyl compound, n isa number from 0 to 5, and each R is independently a group selected fromthe class consisting of hydrogen, mono valent aliphatic groups having"from 1 to 24 carbon atoms and monovalent aromatic groups having from 6to 18 carbon atoms.

The alcohols from which Z in the preceding formula may be derivedcontain from 1 to 6 hydroxyl groups and from 1 to 24 carbon atoms. Theymay be: open chain compounds such as glycerol and sorbitol or cyliccompounds such as 1,4-p-dimethylolcyclohexane. Among the suitablemonohydric alcohols are methanol, ethanol, octadecanol, etc. Among thesuitable dihydric alcohols are ethylene glycol, hexamethylene glycol,and the polyoxyalkylene gycols in which the oxyalkylene groups have 1 to4 carbon atoms, i.e, the polyoxy-methylene glycols, the polyoxyethyleneglycols, the polyoxypr'opylene glycols, etc. Additional suitable higherpolyhydric alcohols are pentaeythn'tol, arabitol, mannitol, trimethylolpropane, trimethylol ethane, trimethylol methane, inositol, etc.

Suitable esters may also be obtained from aromatic hy= droxy compoundssuch as phenol, the cresols, resorcinal, hydroquinone, naphthol, etc.

In some cases it may be desirable to increase the functionality of theester compounds by linking two or more fatty molecules together. Thiscan be accdr'nplished by reacting a dicarboxylic acid, such as adipicacid or its anhydride, with a suitable amount of diglyceride.Alternatively, naturally occurring glyceride oils may be firstdisproportionated with a polyol, such as pentaerythritol ortrlrnethylolpropane, and then the available hydroxyl groups reacted withpolyfunctional reagents, such as adlpyl chloride,toluene-2,4-diisocyanate, phosphorous oxychloride, etc.

THE MALEYL COMPOUND OR ALPHA, BETA= ETHYLENICALLY UNSATURATED DICARBOXYCOMPOUND While a wide variety of alpha, beta-ethylenically unsaturateddicarboxy compounds, such as maleic acid, fumaric acid, dimethylmaleate, dibutyl maleate, monomethyl hydrogen maleate, mono-2-ethylhexylhydrogen maleate, citraconic acid, citraconic anhydride, itaconic acid,itaconic anhydride, ethyl maleic acid, maleimide, maleamic acid, etc.,can be used in this invention, maleic anhydride is the preferreddicarboxy compound because of (1) its low cost (2) the ease with whichit forms adducts in almost quantitative yields and (3) the highconcentration of amide groups which result from the reaction of theanhydride adduct with a basic nitrogen compound. Maleic anhydride isdecidedly superior to all of the above compounds. For example, maleicacid, which forms the anhydride under the maleation reaction condition,is twice as expensive as maleic anhydride; and fumaric .acid, whichapproaches the cost of maleic anhydride on a weight basis, requiresconsiderably more severe reaction conditions to form an adduct in loweryields. Further, adducts prepared from free dicarboxylic acids that arenot capable of forming an anhydride under the conditions of themaleation reaction, and from halfesters and diesters contain a lowerconcentration of amide groups after treatment with a suitable basicnitrogen com pound than adducts containing the same concentration ofcarboxy groups in the anhydride form. It goes without saying thatdiesters are only suitable in this invention when at least some of thecarboxy groups in the diester adduct are saponified. during or beforethe addition of the basic nitrogen compound. Citric acid and malic acidwhich form alpha, beta-ethylenically unsaturated dicar boxy compoundsunder the conditions of the maleation reaction can also be used in thisinvention.

THE BASIC NITROGEN COMPOUND Ammonia, which can be employed as gaseousammonia or in the aqueous ammonium hydroxide form, is the preferredbasic nitrogen compound because of its low cost, availability, highvapor pressure in water, the ease with which it forms amides and theease with which its amides form methylol groups. Various primary amines;such as methyl amine, ethyl amine and butyl amine; primary and secondarypolyamines; such as ethylene diamine, diethylene triamine, propylenediamine and N,N- dimethyl-ethylene diamine; can be used to partially orcompletely replace ammonia. All of these amines contain at least twoactive hydrogen atoms which may be bonded to the same or to differentnitrogen atoms in the same molecule.

FORMALDEHYDE SOURCE Formaldehyde, generally as Formalin, is thepreferred source of formaldehyde. Polymeric forms of formaldehyde, suchas trioxane and paraformaldehyde, are de-= cidedly inferior toformaldehyde. These polymeric forms must be employed at much highertemperatures than the monomeric formaldehyde. Of course, the polymericform is equivalent to the monomeric form if it is first converted to themonomeric form before addition to the amide adducts. If inhibitedFormalin, which contains methanol, is employed some of the R groups willbe methyl groups. Reaction products of formaldehyde with basic nitrogencompounds of the preceding paragraph are generally poorer than if theindividual reactants are added. Condensates of this type, such ashexamethylene tetramine, are not suitable as a source of bothformaldehyde and ammonia in the absence of water. Even in those caseswhere ammonia has been employed to form the amide prior to the additionof hexamethylene tetramine, higher temperatures are required to form thedesired methylol amide than when monomeric formaldehyde is used.Further, the methylol amide products prepared with formaldehydecondensation products are inferior in many end uses to the methylolamideproducts prepared from monomeric formaldehyde, particularly where awater-insoluble, detergent resistant coating is desired. Other thingsbeing equal, it has been found that films cast from methylol amidesprepared by reacting maleated oil with hexamethylene tetramine absorbwater (are swelled by distilled water) when immersed for 2 or 3 hourswhereas films cast from methylol amides prepared in the preferred mannerdo not swell or absorb water.

NEUTRALIZING BASE Any of the aforementioned basic nitrogen compounds(ammonia, primary monoamines, primary polyamines or secondarypolyamines), secondary amines such. as diethylamine, morpholine;tertiary amines such as triethyl amine, methyl diethanol amine;quaternary amines such. as tetramethyl ammonium hydroxide; inorganicbases, such as sodium hydroxide or potassium hydroxide, can be employedto neutralize the methylol amide adducts. The choice of neutralizingbase has a decided effect on the properties of the cured methylol amideadducts. For example, other things being equal, cured films preparedfrom methylol amides, neutralized with a volatile base, particularlyammonia, have better resistance to water, dilute alkali, and organicsolvents than films made from methylol amides neutralized with anon-volatile inorganic alkali, such as sodium or potassium hydroxide.

MALEATION STEP In somewhat greater detail the maleation step is carriedout by reacting the long chain ethylenically unsaturated fatty compoundand the alphabeta-ethylenically un saturated dicarboxy compound at atemperature of about C. to 300 C. The long chain fatty compound and thedicarboxy compound can be mixed together and heated to the desiredreaction temperature. Alternatively, the dicarboxy compound can be addedin increments to the long chain fatty material while the latter ismaintained at the desired reaction temperature. The continuous additionmethod is preferred because it is easier to control and reproduce,particularly when maleic anhydride is employed. When a batch method isemployed using maleic anhydride, the batch temperature must be carefully controlled in order to prevent foaming and sublimation of themaleic anhydride. When the continuous addition method is used the rateat which maleic anhydride is added can be adjusted so that there islittle or no refluxing.

This reaction may be carried out at atmospheric pressure in an openvessel or under pressure in an autoclave. Maleic anhydride forms anadduct in almost quantitative yields in an open vessel and accordinglysealed reactors are not necessary. For example, when maleic anhydridewas reacted with soybean oil in a 3-mole-to-1-mole ratio at from about230250 C., an average of'97.4% of the maleic anhydride was converted tothe adduct. At a temperature of about 18()210- (3., an average of 88.6%of the maleic anhydride was converted to the adduct. Other dicarboxycompounds, which are less efficient adduct formers, give higher yieldswhen a sealed system is employed. For example, dibutyl maleate, whichyields the desired adduct in about 3040% of the theoretical yield in anopen reactor, can be converted to the desired adduct in considerablyhigher yields by carrying out the reaction under pressure.

The efliciency of the maleation reaction of maleyl compounds, such asdibutyl maleate, with non-conjugated polyunsaturated materials can alsobe increased by providing an isomerization catalyst for the long chainpolyunsaturated fatty material, i.e., a catalyst which converts twonon-conjugated double bonds, such as in linoleates, to a conjugateddiene system. In such case the maleation reaction is primarily aDiels-Alder type addition. A combination of pressure and fattyisomerization catalyst is usually the best means of increasing theefficiency of adduct formation between non-conjugated long-chainpolyunsaturated compounds, particularly linoleic and linolenic acidesters, and the less efiicient dicarboxy compounds.

The isomerization of two unconjugated ethylenic double bonds inlinoleates also takes place without any isomerization catalysts duringthe maleation reaction. For example, when maleic anhydride is reactedwith a glyceride oil rich in linoleates, such as soybean oil and linseedoil, approximately one-third of the adducts formed seem to be byDiels-Alder addition. The number of adducts formed by Diels-Alderreaction can be calculated by determining the number of ethylenic doublebonds in the starting long-chain fatty material and in the finalproduct. As explained above (see Equation No. II) an ethylenic doublebond in the fatty material is lost each time a Diels-Alder adduct formswhile no loss of unsaturation accompanies the formation of the principaladduct formed according to Equation I.

The ratio of alpha, beta-ethylenically unsaturated dicarboxy compound toethylenically unsaturated long chain fatty compound in the reactionvessel can range from about 0.1 to 2 moles or more of dicarboxy compoundper equivalent of unsaturation in the unsaturated long-chain fattycompound depending upon the choice of reactants and the desiredproperties of the products. For example, the preferred naturallyoccurring glyceride oils, such as soybean oil or linseed oil, can bereacted with from about to 45% by weight of maleic anhydride to formadducts containing from about 0.5 to 4.5 maleic anhydride moieties permolecule of glyceride oil. (The resulting maleic anhydride portion oftheglyceride oil adduct comprises from about 5% to 33% by weight of theproduct.) The properties of the various members vary as follows,depending upon the level of maleation.

Maleated glyceride oils, which contain in excess of about 5% by weightmaleic anhydride or about 0.5 mole of anhydride per mole of glycerideoil, form stable suspensions in aqueous ammonium hydroxide while thosecontaining in excess of about 14% by weight maleic anhydride or about1.5 moles of anhydride per mole of glyceride oil are soluble in aqueousammonium hydroxide. Methylol amides at the same level of maleation haveessentially the same dispersibility characteristics in aqueous base asthe anhydride adduct from which the methylol amide is formed. Otherthings being equal, thin layers of fully cured glyceride oil methylolamides vary as the suited particularly for use as non-woven binders forwiping cloths (industrial dirt-catching cloths). The methylol amidesbased upon unsaturated fatty acid esters of polyhydric alcoholscontainirig a total of about 4 to 9 poten tially reactive carboxy(carboxylate salt and methylol amide) groups per molecule (preferablyabout 5-7) are particularly useful as the vehicle in organicsolventresistant, detergent-resistant coatings.

It has been found that the addition of about 1% by weight water, basedon the weight of the long-chain fatty material and the dicarboxycompound results in a lighter colored product.

AMIDE FORMATION The maleated adduct of the preceding section can beconverted to the amide by a variety of techniques. For example, ananhydride adduct, such as that resulting from the maleation of anaturally occurring glyceride oil and maleic anhydride or maleic acid,can be converted to the amide form in any of the following ways: 1)stirring the anhydride adduct in an atmosphere of ammonia until theexothermic reaction ceases, (2) addir'fg concentrated ammonium hydroxide(28% aqueous solution, for example), to the anhydride adduct andstirring until the adduct disperses, (3) adding the anhydride adduct tocon centrated ammonium hydroxide and stirring until the ad ductdisperses, (4) mixing the anhydride adduct with a calculated amount ofwater and then bubbling a sufficient amount of ammonia gas into thesystem to disperse the anhydride adduct, (5) mixing the anhydride adductwith a calculated amount of water, opening the anhydride ring by heatingand then adding ammonia gas or aqueous ammonium hydroxide to dispersethe adduct.

It has been found that adding the anhydride adduct to concentratedammonium hydroxide yields the highest conlevel of maleatlon mcrea-ses asfollows:

TABLE I Weight percent Maleate of maleic moieties anhydride per molinthe cule of methylol glyceride amide oil precursor Properties of curedlayer Average total number of potentially reactive carboxy groups permloleeule of glyceride o1 0.5 5 Sticky, oil-like. 1. 0 10 Tacky materialWithout strength. 1. 5 14 Soft, oily, water-resistant film having lowstrength. 1.85 17 Soft, oily, water-resistant film having tair strength.5 2.5 22 Water-resistant film having good strength and solventresistance. 6 3.0 24. 5 Tough, flexible, solvent resistant film. 8.7 4.35 33 Hard, brittle film.

In general, methylol amides having the same total number of carboxylatesalt groups and methylol amide groups (potentially reactive carboxygroups) per molecule will cure to products having essentially the samecharacteristics, provided the methylol amides are prepared in the sameway and cured in the same way. For example, a cured methylol amide basedupon the reaction product of a half-ester of maleic acid and a glycerideoil, which has three half-esterified maleate moieties per molecule ofglyceride oil, has essentially the same properties as a methylol amidebased upon a glyceride oil containing 1.5

'unesterified maleate moieties per molecule. Each of these methylolamides contain a total of three potentially reactive carboxy groups.

The methylol amides based upon unsaturated long chain carboxylic acidesters of polyhydric alcohols containing a total of from about 2 to 4potentially reactive carboxy groups (carboxylate salts and methylolamide groups) per molecule (preferably about 3 to 4) are centration ofamide groups. For example,.when the above illustrative anhydride adduct(glyceride oil and maleic anhydride) is added to a concentrated aqueousammonium hydroxide solution containing two molecules of ammoniumhydroxide per anhydride group in the adduct, about of the anhydridegroups (42.5% of the carboxyl groups) are converted to monoamide groups.The remainder of the ammonium hydroxide is present as the ammonium salt.The concentration of amide groups can be determined by determining theconcentration of non-volatile nitrogen. On the other hand when theammonium hydroxide is added to the adduct in the same proportions, about60% of the anhydride groups (30% of the potentially reactive carboxygroups) are converted to monoamide groups. About 30% of the anhydridegroups (15% of the potentially reactive carboxy groups) are converted tomonoamide groups when concentrated ammonium hydroxide is added to theanhydride adduct of ammonium hydroxide per in a ratio of one moleculeanhydride group.

Still lower yields of amide are obtained if the anhydride ring is openedprior to the addition of ammonium hydroxide. For example, when theanhydride ring of the same adduct is first broken by heating with water,the addition of ammonium hydroxide to the adduct (in a ratio of onemolecule of ammonium hydroxide per anhydride ring) produces only 15% ofamide-containing groups (7.5% of the carboxy groups).

An adduct of a dialkyl maleate, such as dibutyl maleate, can beconverted to the amide form by saponifying off one or both of the alkylgroups followed by the addition of gaseous ammonia or aqueous ammoniumhydroxide. However, the dialkyl maleate adducts are preferably convertedto the amide form by ammonolysis. Ammonolysis techniques are useful forintroducing a reproducible specific number of amide groups into anadduct. Of course such techniques are considerably more expensive thanthe preferred anhydride route.

Adducts based on half-esters of maleic acid may be (1) subjected tosaponification followed by the addition of ammonia or (2) subjected toammonolysis or (3) simply mixed with ammonium hydroxide. If thehalf-ester structure is maintained, cured products based on saidhalf-ester adducts have properties similar to adducts containing thesame number of potentially reactive carboxy groups.

Adducts based on alpha, beta-ethylenically unsaturated imides, such asmaleimide, or upon alpha, beta-ethylenically unsaturated amides, such asmaleamic acid, may be suspended or dissolved in water or aqueousammonium hydroxide in order to be in a suitable state for the additionof formaldehyde. If desired, these materials or the other amide adductsmay be dispersed in organic diluents or solvents such as ethanol,acetone, carbon tetrachloride, etc.

As explained above, in the preceding section the combined number ofcarboxylate salt groups and methylol amide groups (potentially reactivecarboxy groups) per molecule of fatty material has a pronounced effecton the cured methylol amides of this invention. However, the ratio ofamide groups to carboxylate salt groups has less effect on the curedmethylol amides than the total of potentially reactive carboxy groups.For example, cured methylol amides based upon glyceride oil adductshaving on an average 0.9 amide groups and 5.1 carboxylate salt groupsper molecule have properties quite similar to cured methylol amidesbased upon glyceride oil adducts having on an average from about 1.8 toabout 2.6 amide groups and correspondingly 4.2 to 3.4 carboxylate saltgroups (6 potentially reactive carboxy groups) per molecule. Otherthings being equal, while all of these products can be cured by heat toform water-resistant coatings, the latter products have somewhat betterdetergent resistance, solvent resistance and higher tensile strength.Accordingly, products having higher ratios of amide groups tocarboxylate salt groups are preferred. However, even those productshaving lower ratios of amide groups to carboxylate salt groups formmethylol amides having excellent properties as paint primers, etc.

METHYLOL AMIDE FORMATION The amide adduct of the preceding section,which has preferably been dispersed in water, is then reacted withformaldehyde or a compound capable of generating formaldehyde,preferably by adding the formaldehyde source (usually formalin orparaformaldehyde depolymerized to the monomeric form) to the amideadduct or by adding the amide adduct to the formaldehyde source. Thisreaction can be carried out in a sealed vessel or in an open vessel.Generally, it is preferred to carry out this reaction at moderatetemperature C. to 75 C.) in an open vessel.

As pointed out above, a principal object of this invention is to providea series of water-dispersible methylol amide adducts which can be curedby heat to form water-- resistant, detergent-resistant materials. Inorder to form materials of this type, a suflicient concentration offormaldehyde is added to the aqueous amide adduct composition to provideat least about 0.7 mole of formaldehyde per each equivalent of nitrogencontaining compound bearing a nitrogen atom bonded directly to hydrogen(each NH group) in the aqueous composition, thereby converting freeammonium ions, primary amine groups, etc. to methylol amine groups.Excellent results have been obtained by adding at least about 0.8 moleof formaldehyde for each mole of basic nitrogen containing compound,which contains two hydrogen atoms bonded directly to nitrogen, used toform the amide, as set forth in the preceding section. In this wayessentially all the ammonium ions, etc. in the reaction medium areconverted to non-volatile nitrogen and the methylol amide adduct isprecipitated from the aqueous reaction medium as a Water-insolublehydrate. This frequently has a dough like consistency. The formation ofthis precipitate is visual evidence that a sufiicient concentration offormaldehyde has been added to the amide aduct.

Less than 0.8 mole of formaldehyde per each mole of basic nitrogencompound, which contains two hydrogen atoms bonded directly to nitrogen,used to form the amide, as set forth in the preceding section, willprecipitate the methylol amide if the basic nitrogen compound used toform the amide is volatile and some or all of the volatile material islost or distilled from the aqueous amide adduct composition prior to theaddition of formalde hyde.

While the formation of a methylol amide precipitate is an excellentmeans of determining whether the methylol amide will have the mostadvantageous curing properties, large-scale production of the product isfacilitated by maintaining the methylol amide in solution during theaddition of the formaldehyde. Precipitation of the methylol amide fromthe aqueous reaction mixture can be avoided without sacrificing any ofits curing properties by adding a basic material, which does not reactwith formaldehyde, to the adduct prior to or at the same time as theformaldehyde is added. For example, a volatile tertiary amine, such astrimethyl amine or triethyl amine, can be added to the adduct for thispurpose, as can sodium carbonate, tetramethylammonium hydroxide, or thelike. This basic material buffers the methylol amide solution so thatthe methylol amide is less prone to precipitate. Generally, when analkali such as sodium carbonate is employed, it is advisable to add anequivalent concentration of an acid substance, such as ammonium chlorideor hydrochloric acid, later in the process. If desired, a basic compoundcontaining groups reactive with formaldehyde, such as ammonia, may beemployed in the same manner. However, extreme care must be taken inorder to add enough formaldehyde to give the methylol amide the mostdesirable curing properties without precipitating the methylol amide.

If less than 0.7 mole of formaldehyde per each equivalent ofnitrogen-containing compound bearing an NH group is added to the aqueousamide adduct, the heatcured methylol amide has poorer water resistanceand detergent resistance. In fact, the water resistance and de= tergentresistance is in some cases only slightly better than that of thecomparable amide adduct, which has not been reacted with formaldehyde.Generally speaking, the methylol amides which have not been treated witha sufficient concentration of formaldehyde are best suited for useswhere the curing characteristics of the methylol amide are relativelyless important, such as in starch warp sizing compositions.

After the formaldehyde reaction, the resultant methylol amide adduct isneutralized or made basic by the addition of a suitable basic material,preferably ammo-- nium hydroxide or a volatile amine. Any precipitatedmethylol amide is thereby redispersed.

Non-volatile alkali is not preferred because, as pointed out above, thecured products have poorer water resistance and detergent resistance.Diamines, such as ethylene diamine, are advantageously employed withammonia in order to give the cured products a somewhat softer, moreflexible character.

HEAT CURING METHYLOL AMIDES The various methylol amides of thisinvention fall into roughly two classes, which are (1) those methylolamides which have relatively poor heat-curing properties due to suchfactors as a low level of potentially reactive carboxy groups, reactionwith an insuflicient concentration of formaldehyde or the use of anon-volatile alkali to neutralize or redissolve the methylol amideprecipitate and (2) those methylol amides which have good heat-curingproperties. Of these, the latter are preferred, although both groups areuseful as indicated before. The preferred, heat-curing methylol amidesare adducts of maleic anhydride or maleic acid with ethylenicallyunsaturated carboxylic acid esters of polyhydric alcohols (preferablynaturally occurring glyceride oils such as linseed oil or soybean oil)which contain from about 2 to 9 potentially reactive carboxy groups permolecule. The methylol amides based on the long chain fatty acid estersof polyhydric alcohols having esterified ethylenically unsaturated fattyacid chains of from to 24 carbon atoms are solu ble in aqueousammoniacal solutions when said adducts contain on an average at leastabout 1 potentially reactive groups per each esterified fatty acid chainof from 10 to 24 carbon atoms.

As pointed out above, completely cured adducts containing about 2-4(preferably 3-4) potentially reactive carboxy groups have an oily ortacky surface, which makes them useful as non-woven binders forindustrial dirt or dust wiping cloths. Non-woven dust-wiping clothsbased on methylol amides having less than 3 potentially reactive carboxygroupsare decidedly inferior in strength and in blocking characteristicsto wiping cloths based on methylol amides having three or morepotentially reactive carboxy groups. Best results have been obtainedwhen the non-woven wiping cloth is based on a methylol amide containing3.54 potentially reactive carboxy groups per molecule.

Fully cured methylol amides having from about 5 to 7 potentiallyreactive carboxy groups per molecule have the best combination oftensile strength, flexibility, water-resistance, detergent-resistance,organic solvent resistance 50 and freedom from tack onoiliqess. Theseadducts are useful as non-woven binders, backings for carpets,automobile upholstery, etc.; as the principalyehicleior paintsor paintprimers; as nylon or polyester tire cord adhesives,

as water-proofing top coats for awnings; as water-proof ing additives tostarch and polymer latices (polyvinyl acetate for example); inkvehicles; lubricants for rolling steel that on curing serves ascorrosion resistant coatings,

etc.

Cured methylol amides having on an average about nine potentiallyreactive carboxy groups per molecule are too brittle for some uses, butthe flexibility can be improved by adding unsaturated fatty acids, suchas oleic acid or tall oil acids, to the methylol amide either before orafter the maleation step.

The various heat-curing methylol amides can be cured completely in lessthan 10 minutes at 150 C., 20 minutes at 140 C., and 40 minutes at 120C. In general, these materials need temperatures in excess of 90 C. inorder to get a complete cure, but somewhat less than complete cures canbe attained at room temperature. For example, fil'ms cast from aqueousammoniacal solutions of methylol amides, having from about 4.5- to 9potentially reactive carboxy groups per molecule, will air dry to a tackfree surface at room temperature in from about 15 minutes to 1 hour.These films have little water resistance or alkali resistance and areremoved easily after standing at room temperature for'a week or more.However, some of these films based on methylol amides having a highconcentration of methylol amide groups have relatively good waterresistance when allowed to stand for about two weeks or more.

Various catalysts, such as hexamethylene tetramine, ammonium p-toluenesulfonate, ammonium vanadate, ammonium molybdate, boric acid, can beadded to the methylol amides in order to improve one or more of thefollowing properties: (1) the color of the cured product, (2) the speedof cure, or (3) the hardness of the cured vproduct. I

The addition of reactive pigments, such as zinc chromate, to themethylol amide adduct results in a paint composition which air dries atroom temperature to a water-resistant, detergent-resistant coating; Suchpaints also set immediately by plunging freshly painted panels intoboiling water.

It has been pointed out above that'the various methylol amides of thisinvention, which have relatively poor heat-curing properties, aresuitable additives to warpsizing compositions. However, the preferredmethylol amides which have excellent heat curing characteristics arealso preferred in this use, particularly for sizing hydrophobic fibers,such as polyester fiber (polyethylene terephthalate for example), nylon,polypropylene, and

fiber glass. 7 I v A good warp-sizing agent forms a tenacious protectivecoating over the fiber thereby preventingthe fiber from breaking duringthe weaving operation. Various lubricants are also added to the sizingcomposition to cut down friction during the weaving operation andthereby further reduce the possibility of thefiber breaking. Whilestarch and its fractions (amylose and amylop ectin) are excellent warpsizing agents for various natural fibers due toits,

good adhesion to the natural fiber, its poor adhesion. to synthetichydrophobic 'fibers limit its use. Nylon, for example, is usually sized.with the much more expensive acrylic polymers. The preferred methylolamides of this invention have excellent adhesion to'hy'drophobic fibersandit has been found that starch sizing compositionslc on taining thesepreferred methylol amides adhere tenaciously to hydrophobic fiber. Sincethe sizing agents are usu ally removed in alkaline desizing baths afterweaving, the methylol amide is preferably incompletely cured, when thestarch size is applied. If the sizing composition is completely cured,the methylol amide cannot be re= moved in conventional alkaline desizingbaths However, i

the sizingcan'be burnt 01f glass fibers.

The following examples are merelyillustrative and necked flask equippedwith-a stirrer, reflux condenser and addition port. After 294 grams (3moles) of liquid maleic anhydride was added through the addition portover a period of one and one-half hours, the composition was heated to250 C. and held.there for 15 minutes. The maleated oil was cooled toabout 50 C. and then 294.5 grams'of water and. 202.1 grams of aqueousammonium hydroxide (3.1 moles ammonia) were added while maintaining thereactants at between 2550 C, The reactants were stirred until theproduct was a clear solution. It was determined that about 15 percent ofthe potentially reactive carboxy groups (30% of the starting anhydridegroups) had been converted to the amide form by distilling off ammoniafrom a slightly basic sample of the clear solution. Five hundred andfifteen grams of formalin (6.3 moles formaldehyde) were added rapidly tothe amide adduct and the pH of the aqueous system dropped to about 5 to5.5 precipitating the methylol amide as a 15 water-insoluble hydrate.The water-insoluble hydrate was redissolved by slowly adding 223 gramsof aqueous ammonium hydroxide (3.3 moles ammonia) while maintaining theexothermic reaction below about 50 C. Then 21.2 grams ethylene diamine(0.35 mole) and 52.0 grams aqueous hydroxide (0.77 mole of ammonia) wereThe 60% by weight total solids aqueous solution of methylol amide ofthis example was applied as a 1.5 mil film to a series of glass platesand cured in the manner indicated below in Table IV. Each of these filmswere subjected to a series of spot tests. The results are set forthbelow in Table IV.

TABLE IV Film Cures= 4 Min. 120 8 Mill. 120 C. 15 Min. 120 C. 4 Mill.150 (J. 8 Mill. 150 C. 15 Min. 150 C.

Time Efiect Time Effect Time Effect Timo Effect Time Effect Timc Efitct0.5% Dash Detergent 18 min. T 50 min.-. T 4 hr... R l051ni11 T 4 hr... R4 hr... N Ivory Soap. 18 min... T 50 min... T +4 hr... R 105 min.. '1 4hr... R 4 hr... N CCli 3min. T 4hr... E 4 hr... E 4 hr-.. E 4 hr--. E 4hr--- N 2% HCl 18 min... '1 4 hr..- C 4 hr... N 4 hr... 0 4 hr..- N 4hr. N 2% H3804...... min... T 4 hr... 0 4 hr... N 4 hr... C 4 hr... N 4hr... N Tap Water 20 min... '1 4 hr... C 4 hr... N 4 hr.-. C 4 hr--. N 4hr N Bleach 18min-.- T min... T 50min... T 38min... T 3 hr.-. T 4 hr. TPerchloroethylene 3min.- T 4 hr E 4 hr E 30min..- T 4 hr 4 hr E KEY.T=Through the Film; R=Raised; E=Etched; C=Col0red; N=No Effect.

added to adjust the pH of the aqueous solution of methylol amide to a pHof 7.58.5.

The 60 percent by weight total solids aqueous solution of methylol amideof this example was applied to glass plates with a Bird applicator andcured at 150 C. for eight minutes. The results are set forth below inTable II.

TABLE II Film Thickness in mils Test 1.5 mil 2 mil Tensile Strength,p.s.i 850 875 Tensile Modulus, p.s.i 12,800 40,700 1 Percent Elongation34 30 30 Weight Loss after 300 Revolutions on Taber Abrasor, mg 35 35Sward Hardness 14 14 EXAMPLE II 35 Eight hundred and eighty-four gramsof bleached soybean oil (1 mole) was heated to 230 C. in a three-neckedflask equipped with a stirrer, reflux condenser and addition port. After294 grams (3 moles) of liquid maleic anhydride was added through theaddition port over a period of one and one-half hours, the compositionwas heated to 250 C. and held there for 15 minutes. The maleated oil,cooled to about 50 C., was then added to 700 grams of aqueous ammoniumhydroxide (6 moles ammonia) while maintaining the reactants at between25- 50 C., thereby dissolving the maleated oil. It was determined thatabout 42.5% of the potentially reactive carboxy groups (85% of thestarting anhydride groups) had been converted to the amide form bydistilling off ammonia from slightly basic sample of the solution. Fivehundred and fifteen grams of formalin (6.3 moles formaldehyde) wereadded rapidly to the solution and the pH of the aqueous system droppedto about 5 to 5.5 precipitating the methylol amide as a water-insolublehydrate. The water-insoluble hydrate was redissolved by slowly adding143 grams of aqueous ammonium hydroxide (21 moles ammonia) whilemaintaining the exothermic reaction at about 50 C. The solution had a pHof about 7. Then 21.2 grams ethylene diamine (0.35 moles) and 52.0 gramsaqueous ammonium hydroxide (0.77 mole ammonia) were added to adjust thepH of the aqueous solution of methylol amide to a pH of 7.5-8.5.

The 60% by weight total solids aqueous solution of methylol amide ofthis example was applied to glass plates with a Bird applicator andcured at 150 C. for eight minutes. The results are set forth below inTable III.

The above table indicates that the methylol amides of this invention canbe cured under varying conditions to form water-resistance, detergentresistance, organic solvent resistant coatings. The table also indicatesthat the degree of resistance is dependent upon the cure temperature andcure time.

EXAMPLE III This example illustrates the preparation of a maleated oilsuitable for use as a non-woven binder for industrial dusting cloths.The methylol amide was prepared by the method of Example I by reactingin order 884 grams of bleached soybean oil (1 mole), grams maleicanhydride (1.53 mole), 258.5 grams water, 177.8 grams aqueous ammoniumhydroxide (2.6 moles ammonia), 452.9 grams formalin (5.6 molesformaldehyde), 204 grams aqueous ammonium hydroxide (3 moles ammonia),18.6 grams ethylene diamine (0.3 mole) and 45.5 grams aqueous ammoniumhydroxide (0.7 moles ammonia).

The 60% by weight total solids aqueous solution of methylol amide havingon an average about 3 potentially reactive carboxy groups per glyceridemolecule was ap plied to a glass plate with a Bird applicator and curedat 150 C. for eight minutes. The film was soft, oily, waterresistant andhad little tensile strength.

EXAMPLE IV Example III was repeated except that the concentration. ofmaleic anhydride was increased to 1.85 moles. This product whichcontained on an average about 3.7 potentially reactive carboxy groupsper molecule was better suited for use as a non-woven binder forindustrial dusting cloths because of the cured products decidedly bettertensile strength.

EXAMPLE V Example III was repeated except that the concentration ofmaleic anhydride was decreased to 1.1 moles. This product, whichcontained on an average about 2.2 potentially reactive carboxy groupsper molecule, was inferior to the product of Example III as a binder fornon-woven industrial wiping cloths since the methylol amide waswater-dispersible and not water-soluble and the cured product hadvirtually no strength and tended to block.

EXAMPLE VI A maleated oil was prepared by the method of Example I using2,500 grams bleached soybean oil (2.83 moles) and 1,232 grams maleicanhydride (12.54 moles). Three hundred grams of this maleated oil (0.23mole oil) having on an average about 8.8 potentially reactive carboxygroups per molecule (4.4 anhydride moieties per molecule) was mixed with200 grams of water and then sparged with ammonia gas until the maleatedoil dissolved and the reaction mixture had a pH of about 7; thetemperature of the reaction mass reaching a peak temperature of about 77C. The reaction mass was cooled to 50 C. and then 100 grams of formalin(1.27 moles formaldehyde) was added precipitating the methylol amide asa hydrate. The methylol amide was redissolved by sparging the reactionmixture with ammonia gas until the aqueous solution had a pH of 7.5. A1.5 mil film of this material was prepared in the manner described inExample I. This film was extremely hard, water-resistant,detergent-resistant, but somewhat brittle.

EXAMPLE VII Eight hundred grams of maleated soybean oil prepared by themethod of Example VI having on an average 4.4 anhydride moieties permolecule and 800 grams of maleated soybean oil prepared by the method ofExample III having on an average 1.5 anhydride moieties per moleculewere mixed with 1,400 grams water and sparged with ammonia until themaleated oil dissolved. Four hundred and fifty'grams formalin (5.55moles formalde= hyde) were then added precipitating the methylol amideas a cloudy material. The methylol amide was redissolved by spargingwith ammonia gas until the aqueous solution had a pH of about 7.5. Acured film was prepared from this composition in the manner described inExample I. The cured film did not have the brittleness of the product ofExample VI nor the oiliness of the product of Exam= ple III. Instead thecured film had properties similar to the films prepared in Example I.

EXAMPLE VIII Eight hundred and eighty-four grams of linseed oil (1 mole)was reacted with 294 grams maleic anhydride (3 moles) in the mannerdescribed in Example I. The methylol amide was prepared by the method ofExample I by reacting in order 125 grams of maleated linseed oil 1%EXAMPLE X Example IV was repeated except that the starting glyceride oilcomposition was 174 grams linseed oil and 710 grams soybean oil.

EXAMPLE XI This example illustrates that the methylol amides of thisinvention are suitable vehicles for paints. The methylol amides ofExamples I, II, IX and X were all tested in the following formulation:

Pounds Red Iron Oxide R-8098 (C. K. Williams Co.) 150 Barytes W-1430 VVF(C. K. Williams Co.) 150 USP-400 1 (minerals+pigmentsPhillips Corp.) 150Methylol amide (60% total solids) 375 Water 295 1A magnesium silicateextender.

The paints were prepared by mixing all of the pigment with the methylolamide and then placing on a three-roll mill. After one pass on the rollmill, the dispersions had a North Fineness of Grind of 7. The pigmentpastes were allowed to stand for 24 hours and then diluted with Water tospray viscosity of from 1824 seconds as measured in a No. 4 Ford Cup.The paints were sprayed on cold-rolled steel and Bonderite 100 (zincphosphate coated) steel panels, flash-dried for thirty minutes, baked at350 F. for 20 minutes and then sanded to a dry film thickness of between0.8 and 1.2 mils. The panels were then topcoated with Ford Cotor CompanyM301 Black Enamel and flash dried for thirty minutes. The panels (induplicate) were then exposed to 90 F. distilled water for 500 hours andtested for impact resistance. The results are below in Table V.

TABLE V 500 Hours-90 F. Water Test Primer Alone Primer+Topcoat DireetImpact Methylol Amide Primerri-Topcoat of Example Cold-Roll BonderiteCold- Roll Bonderite Bonderite I Failed 288 hours- S1. discoloration...Fine blisters; Fine blisters; lbs.

loss of gloss. loss of gloss.

II Sl. discoloration..- Excellent Pinholes Very good 45 lbs.

IX Failed 288 hours. S1. discoloration Fine blisters Fine blisters 45lbs.

X Failed 500 hours. Very good... Very good 45" lbs.

Ford Motor Co. Prim Excellent Excellent--. Pinholes 45 lbs.

EXAMPLE IX Example I was repeated except that the maleated soybean oilwas added to 496.6 grams of aqueous ammonium hydroxide (3.1 molesammonia) instead of adding 294.5 grams water and 202.1 grams of aqueousammonium hydroxide (3.1 moles ammonia) to the maleated soybean oil. Itwas determined that about 22.5% of the potentially reactive carboxygroups (45% of the starting anhydride groups) had been converted to theamide form. Cured methylol amides based on the product of this ex amplewere similar to the cured methylol amides based on the product ofExample I.

The data in Table V indicates the methylol amides of this invention areall suitable for use as paint vehicles with the methylol amide ofExample II being best, followed by the methylol amide of Example X, themethylol amide of Example IX and the methylol amide of Example I.

Panels coated with paints based on the methylol amides of Examples IIand X, which had passed the stringent Ford Motor Company 500 hour900 F.water test, were then subjected to 250 hours of salt-fog exposure. Thefogged panels had higher impact resistance than fogged panels based onthe Ford Motor Company primer.

EXAMPLE XII Example I was repeated except that the 884 grams of soybeanoil was replaced by a mixture of 663 grams of soybean oil and 210 gramsof tall oil fatty acids. Cured films based on the methylol amidecomposition of this example had better flexibility than those based onthe methylol amide of Example I.

EXAMPLE XIII Example I was repeated except that the 884 grams of soybeanoil was replaced by 840 grams of tall oil fatty acids (3 moles). Curedfilms based on the methylol amide of this example were quite similar(soft, flexible,

low strength) to the films prepared from the methylol amide of ExampleIII and IV.

EXAMPLE XV reacted in order with 25 grams water, 8.1 grams ethanol amineat 100 C., 43 grams of formalin (0.5 mole formaldehyde) at 60 C. and11.2 grams of ethanolamine. A 1.5 mil film cured at 150 C. for tenminutes had good water-resistance and detergent resistance.

EXAMPLE XVI This example illustrates that the methylol amides of thisinvention can contain chloro and hydroxyl groups. One hundred grams of amaleated soybean oil (0.085 mole) having on an average 6 potentiallyreactive carboxy groups per molecule (3 anhydride moieties per molecule)was treated with 50 ml. of a saturated aqueous Halane solution(1,3-dichloro-5,S-dimethylhydantoin) which reacted at the double bondsof the maleated soybean oil to form vicinal chlorohydroxy groups. Theaqueous composition was sparged with ammonia gas until the reactionmedium was neutral. The amide adduct was precipitated from solution inthe form of the methylol amide by the addition of 30 ml. of formalin andthen redissolved by sparging with ammonia gas until a pH of 7 wasreestablished. A 1.5 mil film cured at 150 C. for 10 minutes had goodwater-resistance, detergent resistance, flexibility and tensilestrength. It was similar to the cured film prepared in Example I.

A. somewhat softer film resulted when the saturated Halane solution wasreplaced by 30 ml. of 4.1 titer chlorine bleach. The softness wasprobably due to the sodium ions in the bleach.

EXAMPLE XVII This example illustrates the preparation of a methylolamide using hexamethylenetetramine. Three hundred and ninety-two gramsof a maleated soybean oil (0.33 mole) having on an average 6 potentiallyreactive carboxy groups per molecure (3 anhydride moieties permolecule), 90 grams of hexamethylene tetramine (0.64 mole) and 300 ml.of water were heated at 70 C. until a cloudy product having a pH of5.5-6.0 was formed. During the heating at least part of thehexamethylene tetramine broke down into ammonia and formaldehyde, whichwas indicated by the liberation of. formaldehyde vapors, ammonia vaporsand the partial dispersion of the amide adduct. The product dissolvedcompletely on the addition of ml. of ammonium hydroxide, which broughtthe pH of the methylol amide composition to 7. A 1.5 mil film cured at150 C. for ten minutes was softer than the cured film of Example I.Further, when a cured film of Example I and a cured film of this examplewere immersed in water, the film prepared from the product of thisexample had absorbed water and softened noticeably after two hours. Onthe other hand the cured film based on the product of Example I wasstill clear and hard after over 100 hours. Apparently the product ofthis example does not cure as fully as the products prepared by thepreferred route.

EXAMPLE XVIII This example illustrates that hexamethylene tetramine isnot a suitable source of both ammonia and formaldehyde in the absence ofwater. One hundred and twenty-five grams of a maleated soybean oil (0.11mole) having on an average 6 potentially reactive carboxy groups permolecule (3 anhydride moieties per molecule) and grams hexamethylenetetramine (0.18 mole) were mixed together and heated in an autoclave at115 C. A small sample smelliing strongly of formaldehyde was cooled toroom temperature. This sample was dark and insoluble in water. Six ml.of water was added to the hot autoclave and a violent frothing started.The exothermic reaction raised the reaction temperature to 122 C. Onehundred and forty-four ml. of water were added to the cooled adductwhich dissolved when the aqueous medium was adjusted to pH 7.

EXAMPLE XIX' This example illustrates that the product prepared by themethod of Example 8 of U.S. Patent 2,188,890 is completely unlike theproducts of this invention. Seventy grams of a maleated soybean oil(0.07 mole) having on an average 3.7 potentially reactive carboxy groupsper molecule (1.85 anhydride moieties per molecule), 14 gramshexamethylene tetramine (0.1 mole) and 46 grams of commercial xylenolswere heated slowly in a stainless steel resin kettle to C. The reactionstarted slowly as evidenced by bubbling and evolution of steam. A samplewas taken and allowed to cool to room tempera.- ture. The sample was atough pliable resin which was insoluble in aqueous ammonium hydroxide.The main reaction products were slowly heated to 200 C. until a varyhard resin solidified which was insoluble in aqueous ammonium hydroxide.Neither of the reaction products of this example had thewater-dispersibility of the products of my invention.

EXAMPLE XX This example illustrates the preparation of a methylol amidebased on a pentaerythritol tetraester of soybean oil fatty acids. Thepentaerythritol tetraester of soybean oil fatty acids was prepared byrefluxing 15 grams of pentaerythritol tetraacetate (0.049 mole) and 58.4grams of soybean oil methyl esters (0.21 mole) in the presence of 1.05grams sodium methoxide. The stripped pentaerythritol tetraester ofsoybean oil acids had a hydroxyl value of 0.3 milliequivalent per gramand saponification value of 179.

Twelve and six-tenths grams of pentaerythritol tetraester of soybean oilacids (0.01 mole) and 3.9 grams of maleic anhydride (0.04 mole) wereheated at 230 C. for one hour under reflux. The product was stripped andthen cooled. It contained on an average 1.5 maleic anhydride moietiesper molecule. The product was then dispersed in aqueous ammoniumhydroxide, which contained 0.08 mole ammonia; precipitated with 0.08mole formalin; and neutralized to pH 8.5 with aqueous ammonium hydroxidein the manner described in Example II. The resulting aqueous dispersionwas a clear red brown, viscous fluid.

A 3 mil film of the methylol amide of this example was prepared in themanner described in Example I except that the film was heated at 150 C.for ten minutes. The soft, flexible filrn was similar to the filmprepared in Ex ample IV.

A somewhat harder film resulted when a 10 gram sample of the 60% byweight dispersion was compounded with lead naphthenate (.0067% by weightlead based on the weight of the dispersion), manganese naphthenate(.0067% by weight manganese base-d on the weight of the dispersion) andcobalt naphthenate (.0067% by weight cobalt based on the weight of thedispersion), applied to a glass plate and then cured at 150 C. for tenminutes. A very hard film resulted when the above driers were replacedwith ferric naphthenate (.02% by weight iron based on the weight of thedispersion).

EXAMPLE XXI This example illustrates the preparation of a methylol amidebased on an isomerized glyceride oil. Example II was repeated exceptthat the starting glyceride oil was isomerized by heating at 230 C. fortwo hours with 2% anthraquinone based on the weight of oil and thenfiltered in order to remove the anthraquinone. The spectral absorptionof the soybean oil at 2,350 millimicrons (diene structure) increasedfrom 0.4 to 18.4 indicating that approximately 30% of linoleic acidmoieties in the soybean oil had been conjugated.

A film prepared in the manner described in Example I was harder than afilm based upon the methylol amide of Example II.

EXAMPLE XXII This example illustrates the use of itaconic acid in placeof maleic anhydride. One hundred and sixty grams of soybean oil (0.18mole) and-73 grams of itaconic acid (0.56 mole) were heated withstirring to 170 C. until the evolution of water vapor stopped, whichindicated that the itaconic acid had been converted to the anhydrideform. The temperature was slowly increased to 225 C. over a 1 /2 hourperiod and thenheld at 225 C. for two hours. On cooling a dark resinousmaterial settled from the oil phase and the supernatant oil phase wasseparated. The oil adduct contained on an average 0.9 mole of maleylmoieties per molecule or.1.8 potentially reactive carboxy moieties permolecule. The product was then dispersed in aqueous ammonium hydroxide,which contained 0.36 mole ammonia; precipitated with 0.36 mole formalin;and neutralized to pH 8.0 with aqueous amonium hydroxide in the mannerdescribed in Example II.

This product when cured on glass at 150 C. produced a hard brittle,water-insoluble film. The surface of the film was oily, which indicatedthat the product was not completely homogeneous.

EXAMPLE XXIII This example illustrates the preparation of a preferredheat curable methylol amide where the maleated oil is kept in solutionduring all the processing steps. Two hundred grams of a maleated'soybeanoil (0.17 mole) having on an average 6 potentially reactive carboxygroups per molecule (3 anhydride moieties per molecule) were dissolvedin 120 grams of aqueous ammonium hydroxide 1.02 moles amonia) whilemaintaining the reaction vessel below 50 C. After 44.2 ml. of a 25% byweight of aqueous trimethyl amine (0.3 mole) was added to buffer theaqueous amide adduct, 75.6 ml. of formalin (1.02 moles formaldehyde)were added. The aqueous solution had a pH of 6.3 after the addition offormaldehyde was complete. The pH of the solution was then adjusted to 8with aqueous ammonium hydroxide. A cured film was prepared from themethylol amide of this example by heating a coated glass plate at 150 C.for ten minutes. The film had the same properties as a film based on themethylol amide of Example II except that the film from this example wassomewhat lighter in color.

EXAMPLE XXIV Example XXIII was repeated with essentially the sameresults except that the aqueous trimethyl amine and formaldehyde weremixed together and added in a single step.

EXAMPLE XXV The method employed in Example XXIII was repeated exceptthat the trimethyl amine was replace-d by 0.125 mole of an inorganicalkaline material. The results are set forth below in Table VI.

TABLE VI Properties of methylol amide films after heating at Alkali 150C. for 10 minutes NaOH Each of the films had essentially the sameproperties as Na2CO3 the film based upon the methylol amide of ExampleK2003 XXIII except that the films were water sensitive.

The water-sensitivity of these films was overcome by adding anequivalent amount of an acid prpducing salt, such as an aminehydrochloride or ammonium chloride, to the aqueous methylol amide aftertheaddition of formaldehyde and ammonium hydroxide. The pH of the systemwas then adjusted to 8 with aqueous ammonium hydroxide. The results areset forth below in Table VII.

TABLE VII Properties of methylol amide films after heating at 150 C. for10 minutes Moles inorganic Moles acid alkaline material producing salt0.125 NaOH 0.125 NH4Cl Water-insoluble films similar to the film basedupon the meth 0.125 Na CO 0.250 NH4C1.. ylol amide of Example XXIIIexcept that these films are some- O.125 K200 0.250 NH4Cl what harderEXAMPLE XXVI TABLE VIII.ZINC SALT Zinc chromate Zinc Yellow (Zincpotassium chromate) Ammonium Zincate Essentially the same results wereobtained by plunging the coated plate in boiling water.

EXAMPLE XXVII This example illustrates an excellent paint primer whichcures to a water-resistant film in 20 minutes at room temperature or ina few seconds when exposed to live steam. One hundred and thirty-threegrams of the methylol amide of Example II (60% total solids) wasformulated with 250 grams of the following aqueous pigment composition(60% total solids):

Dry weight (grams) Red lead 82.5 Zinc yellow 15.0 Red iron 4....-. 1.5Mg silicate 34.5 Mica n 15.0 Aluminum stearate l... 1.5

The above paint was applied to a steel plate, allowed to dry for twentyminutes and then immersed in distilled water bath which was maintained.at .F. After 360 hours, there was no deterioration in the Surface of thepaint or in the adhesion of the paint to the steel plate.

EXAMPLE XXVIII This example illustrates the compatibility of the meth=ylol amide of Example II with a number of commercially availablepolymers. The methylol amide of Example II (60% by weight total solids)and the various commercially available polymers were compounded on an asis basis and at 20% total solids. The compatibility of the varioussystems is set forth below in Table IX. In the table, the top line, or Aline, represents the as is composition; the bottom line, or B line,represents the composition at 20% total solids. 1" stands forincompatible; PC stands for partly compatible; C stands for compatible;T.S. for total solids and stands for high viscosity.

TABLE 1X Ratio of Methylol Amide of Example II to Polymer Imme- 8 Hrs.on 24 Hrs. at Imme- 8 Hrs. on 24 Hrs. at Imme- 8 Hrs. on 24 Hrs. atdiate Standing 125 F. diate Standing 125 F. diate Standing 125 F.

Darcx 61L (55.8% T.S.) I I PC PC C PC PC Polyvinyl Acetate C I P C 0 PCI C I I Elvacet 81-900 (55% T.S.) C I I C PC PC C PC PC Polyvinyl Ac ateC G O C I I C I I Polycol-694 (55% T.S.). C I I C I I C I I PolyvinylAcetate C C P (J C C PO C P C C- Pliolite Latex 140 (47.5% T.S.). 0 PC IC C C C 0 PC Styrene-60 Butadiene C C C C C C 0 PC C Pliolite Latex 160(48.9% T.S C C I 0 PC PC C PC PC 33 Styrene-60 Butadiene- C C C C C O CP O P C P1i0lite-440 T.S.)- C I I C C C 0 PC PC 35 Styrene-65 ButadieneC I I C C C C PC PC Dylex K-40 (48.9% T.S.) 0 PC PC 0 C C C C C 60Styrene-40 Butadiene. C C C C G C C C C Celanese VX-567 T.S.) C C PC CPC I C PC PC Acrylate O C C C C C C O C Goodrich 450X3 (54.9% T.S.). C 0PC 0 PC I C PC PU Polyvinyl Chloride-Acrylic- C C C G I I C I IHyear-1571 (41% T.S.) C 0* C C C I C C C Aerylonitrile Butadiene. C C CC C C C C C Hyear-2671 (50.3% T.S.) C C PC 0 0 PC" 0 C" C Acrylate C C CC C C C C C Rhoplex HA-8 (46% T.S.) O C C O 0 PC- 0 PC PC Acry te C O CC C C C C C Rhoplex HA-16 (46% T.S.) C C C 0 PC PC C 0 PC Aerylate C C CC O C O C C Rhoplex AO- (55% T.S.) 0 PC PC C 0' PC 0 G O Acrylate C C CC C C O I I Shawinigan 0566 (50% T.S.). C C C 0 PC PC 0 PC PC PolyvinylButyral C C C O P O I 0 PC I Poly-E M C C C C C P C (3 PC P CPolyethylene... C C C C O C C G Since many embodiments of this inventionmay be made and since many changes may be made in the embodimentsdescribed, the foregoing is to be interpreted as illustrative only andmy invention is defined by the n 0 claims appended hereafter.

I claim:

1. The method of preparing a water-dispersible product which comprisesreacting formaldehyde with an aqueous dispersion of an amide adduct of amaleyl compound and an aliphatic compound containing an ethylenicallyunsaturated chain of from 10 to 24 carbon atoms.

2. The method of claim 1, wherein said aliphatic compound containing anethylenically unsaturated chain of from 10 to 24 carbon atoms comprisesat least one compound selected from the group consisting of a fatty acidester, fatty acid, fatty acid N-unsubstituted amide and fatty acid salt.

3. The method of claim 2, wherein said maleyl compound comprises atleast one compound selected from the group consisting of maleic acid andmaleic anhydride.

4. The method of claim 3, wherein said amide adduct comprises anethylenically unsaturated fatty acid ester of a polyhydric alcoholcontaining on an average from about 2 to 9 potentially reactive carboxygroups per molecule.

5. The method of claim 4, wherein said ethylenically unsaturated fattyacid ester of a polyhydric alcohol comprises a glyceride oil.

6. The method of claim 4, wherein at least about 0.7 mole offormaldehyde is added per each equivalent of nitrogen containingcompound having an N-H group.

7. The method of preparing a water-dispersible product which comprisesthe steps of 1) providing an adduct of a maleyl compound and analiphatic compound containing an ethylenically unsaturated chain of from10 to 24 carbons atoms, (2) reacting said adduct with a compoundcontaining a basic nitrogen atom having at least two hydrogen atomsbonded to nitrogen selected from the group consisting of ammonia, aminesand mixtures thereof, and then (3) reacting an aqueous dispersion of thereaction product of step (2) with formal dehyde.

8. The method of claim 7, wherein said compound containing a basicnitrogen atom comprises ammonia.

9. The method of claim 8, wherein said aliphatic compound comprises atleast one compound selected from the group consisting of a fatty acidester, fatty acid, fatty acid N-unsubstituted amide and fatty acid salt.

10. The method of claim 9, wherein said maleyl compound comprises atleast one compound selected from the group consisting of maleic acid andmaleic anhy dride.

11. The method of preparing a Water-dispersible prod uct which comprisesthe steps of (1) providing an adduct of a maleyl compound selected fromthe group consisting of maleic anhydride and maleic acid and analiphatic compound containing an ethylenically unsaturated chain of from10 to 24 carbon atoms selected from the group consisting of a fatty acidester, fatty acid, fatty acid N- unsubstituted amide and fatty acidsalt, wherein said ad duct contains on an average from about 2 to 9potentially reactive carboxy groups per molecule, (2) reacting saidadduct with ammonia and then (3) reacting an aqueous dispersion of thereaction product of step (2) with formaldehyde.

12. The method of claim 11, wherein at least about one-half mole ofammonia is added in step (2) per each potentially reactive carboxy groupin said adduct.

13. The method of claim 12, wherein at least about 0.8 mole offormaldehyde is added in step (3) per each mole of ammonia added in step(2).

14. The method of claim] 12, wherein at least about 0.7 mole offormaldehyde is added in step (3) per each equivalent of nitrogencontaining compound bearing an NH group.

15. The method of claim 14, wherein said aliphatic compound comprises aglyceride oil.

16. The method of claim 15, wherein at least about one mole of ammoniais added in step (2) per each potentially reactive carboxy group in saidadduc:.

17. The method of claim 12, wherein the adduct pro vided in step (1) isadded to an aqueous ammonium hy droxide solution.

18. The method of preparing coated substrates which comprises the stepsof (1) providing an adduct of a maleyl compound selected from the groupconsisting of maleic anhydride and maleic acid and an aliphatic compound containing an ethylenically unsaturated chain of from 10 to 24acid ester, fatty acid, fatty acid N-un= substituted amide and fattyacid salt, wherein said ad the product of step (3) to a substrate anddrying said substrate.

19. The method of preparing a water-soluble product which comprises thesteps (1) providing an adduct of a maleyl compound and an ester; of apolyhydric alcohol with ethylenically unsaturated fatty acid chains offrom to 24 carbon atoms, whereirisaid adduct contains on an average atleast about 1 potentially reactive carboxy group per each esterifiedfatty facid chain, (2) reacting said adduct with a compound containing abasic nitrogen atom having at least two hydrdgen atoms bonded tonitrogen selected from the group consisting of ammonia, amines andmixtures thereof (3) reacting an aqueous solution of the reactionproduct of step (2) with formaldehyde.

20. The method of claim 19 wherein said compound containing a basicnitrogen atom comprises ammonia and said adduct contains at least 3potentially reactive carboxy groups per molecule.

21. The method of claim 20 wherein said maleyl compound comprises acompound .lselected from the group consisting of maleic acid and maleicanhydride, at least about one-half mole of ammonia is added in step (2)per each potentially reactive carboiry group in said adduct and at leastabout 0.7 mole of formaldehyde is added in step 3) per each equivalentof'nitrogen containing compound bearing an NH group in said aqueoussolution.

22. The method of preparing a water-soluble product which comprises thesteps of (1 providing an adduct of a maleyl compound selected from thegroup consisting of maleic acid and maleic anhydride and a glycerideoil, wherein said adduct contain at least 3 potentially reactive carboxygroups per molecule,(2) reacting said adduct with ammonia, wherein atleast about one-half mole of ammonia is added in step .(2) per eachpotentially reactive carboxy group in said adduct, and (3) reacting anaqueous solution of the reaction product of step (2) with formaldehyde,wherein at least about 0.7 mole of formaldehyde is added in step (3) pereach equivalent of nitrogen containing compound bearing an NH group insaid aqueous solution; v

23. The method of claim 22, wherein said glyceride oil comprises soybeanoil.

24. The method of claim 22, wherein said glyceride oil comprises linseedoil.

25. The method of claim 22, wherein said adduct con= tains on an averagefrom 5 to 7 potentially reactive car: boxy groups.

26. The method of preparing coated substrates which comprises the stepsof (1) providing an adduct of a maleyl compound selected from the groupconsisting of maleic anhydride and maleic acid and an ester of a poly=hydric alcohol with ethylenically unsaturated fatty acid chains of from10 to 24 carbon atoms, wehrein said adduct contains on an average atleast about 1 potentially reactive carboxy group per each esterifiedfatty acid chain but no less than about 3 potentially reactive carboxygroups per molecule, (2) reacting said adduct with ammonia, wherein atleast about one-half mole of ammonia is added in step (2) per eachpotentially reactive carboxy group in said adduct, (3) reacting anaqueous solution of the reaction product of step (2) with formaldehyde,wherein at least about 0.7 mole of formaldehyde is added in step (3) pereach equivalent of nitrogen containing compound bearing an NH group insaid aqueous solution, (4) applying a solution of the product of step(3) to a substrate; and (5) drying said substrate.

27. The method of preparing coated substrates which comprises the stepsof (1) providing an adduct of a maleyl compound selected from the groupconsisting of maleic acid and maleic anhydride and a glyceride oil,wherein said adduct contains at least 3 potentially reactive carboxygroups per molecule, (2) reacting said adduct with ammonia, vigherein atleast about one-half mole of ammonia is addtgd in step (2) per eachpoten tially reactive carboxy group in said adduct, (3) reacting anaqueous solution of the reaction product of step (2) with formaldehyde,whg rein at least about 0.7 mole of formaldehyde is added step (3) pereach equivalent of nitrogen containing compound bearing an NH group insaid aqueous solution,'--(4) applying a solution of the product step (3)to a substrate and (5) drying said sub-= StmtEQ 28. The method of claim27 wherein the substrate is dried at a temperature of at least C.

29. A methylol amide having the structure wherein /H OM, 0 1, N

CHgO R and N M is a cation; R R and R are independently selected fromthe group consistiri gj of hydrogen and alkyl; R; and R areindependently selected from the group consisting of hydrogen, halogenand lower alkyl; R and R are each selected from the group consisting ofhydrogen and covalent bonds that taken together, complete a cyclo hexenering.

30. The compound of claim 29 wherein the divalent aliphatic chain offrom 10 to 24 carbon atoms is sub mitted by a carboxylate group.

31. An aqueous dispersion of the compound of claim 29.

32. An aqueous dispersion of the compound of claim 30.

33. A methylol amide of an adduct of a maleyl com= pound and a longchain fatty acid ester of a polyhydric alcohol having an esterifiedethylenically unsaturated fatty acid chain of from 10 to 24 carbonatoms.

34. A methylol amide of a maleated ethylenically unsaturated glycerideoil.

35. An aqueous dispersion of the compound of claim 34, wherein saidcompound contains on an average from 2 to 9 potentially reactive carboxygroups per molecule.

36. An aqueous solution of the compound of claim 34, wherein saidcompound contains an average of at least 3 potentially reactive carboxygroups per molecule.

37. The composition of claim 36 wherein said glyceride oil comprisessoybean oil.

38.. The composition of claim 36 wherein said glyceride oil compriseslinseed oil.

References Cited UNITED STATES PATENTS Coutras.

Kraft.

Phillips et a1 106-264 Evans et a] a 106-253 28 DONALD J. ARNOLD,Primary Examiner J. B. EVANS, Assistant Examiner U.S C1. XR,

} UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,471,466 October 7, 1969 Lester P. Hayes It is certified that error appearsin the above identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 39, "2,491,968" should read 2,941,968 line 43, beginningwith "This application" cancel all to and including "filed Dec. 20,1962." and insert the same at line 21 same column 1 Column 3, lines 65to 67 the formula should appear as shown below:

Column 4, lines 4 to 6, the formula should appear as shown below:

0 0=c c=o Column 5 line 7, "obtain" should read contain line 40"molecule amide groups the higher" should read molecule. In general thehigher Column 14 line 10 "molybdate" should read molbydate Column 18line 33, "Cotor" should read Motor line 58 "900 F. should read 90 F.Column 24, line 74 "10 to 24 acid" should read 10 to 24 carbon atomsselected from the group consisting of a fatty acid Column 26 lines 23 to34 the formula should appear as shown below:

I C: I C

R I c I c CH-A (SEAL) Attest:

WILLIAM E. SCHUYLER, JR. Commissioner of Patents EDWARD M.FLETCHER,JR.Attesting Officer

